Catalytic hydrocarbon conversion



Patented Oct. 14, 1941 CATALYTIC HYDROCARBON CONVERSION Ralph M. Melaven, Highland, Ind., and Rodney V.

Shankland, Chicago, Ill., assignors to Standard Oil Company, Chicago, 111., a corporation of Indiana No Drawing. Application January 19, 1939,

Serial No. 251,738

4 Claims.

This invention relates to a process for the conversion of hydrocarbon oils and particularly to the conversion of heavy hydrocarbon oils such as gas oils, petroleum residuums, hydrocarbon waxes, etc., into lower boiling hydrocarbons, particularly gasoline. The invention relates more particularly to the use of catalysts'for the conversion of heavy hydrocarbon oils at high temperatures. One of the objects of the invention is to utilize a catalyst which will convert a larger amount of the oil into gasoline before it becomes necessary to regenerate it. Another object of the invention is to utilize a catalyst which may be repeatedly regenerated by treatment with an oxygen containing gas for removal of carbonaceous matter without significant loss of catalyst activity. Still another object of the invention is to utilize a catalyst of great physical strength which ,may be employed in granular form without serious disintegration. Other objects will become apparent from the following description.

The catalyst which we employ is prepared in the following manner: A silica gel, so-called, is prepared by adding a,solutin of soluble silicate, for example, sodium silicate, to an excess of strong mineral acid, such as hydrochloric acid or sulfuric acid. We prefer to use sodium silicate solution containing about 15% to 20% of Naz(SiO3) :r. In this formula 0: is unity or greater. The acid employed in making the gel may suitably be about 15% to 25% H2804 and an excess of to 50% may suitably be employed; Other strong 'acids may be used, such as HCl, HNOs, etc. We have sometimes reversed this procedure, however, and added the acid to the silicate solution which causes immediate precipitation. This. method gives a very active catalyst but one of low mechanical strength.

After adding the silicate solution to the acid, and mixing, it is allowed to stand and soon the solution solidifies to a jelly. This is broken up by agitation and washed in running water until substantially all the acid and soluble salts are removed. Considerable time is-requiredto permit all the salts to diffuse'from the pieces of jelly and the washing operation is facilitated by employing hot water or by digestionand boiling. The gel is then separated from the water and dried. It nowresembles an irregular sand and at this stage it is crushed and screened to remov particles which" are too fine for ultimate use. The gel so prepared is characterized by possessing a submicroscopic pore structure which provides an enormous amount of pore surface accessible only to those materials which can free- 1y penetrate thepores and gain access to the interior of the grains.

and finally washed until the water gives no further test for acid ion. ,Also, the gel may be further washed with distilled water after final drying.

The next step in the preparation of the catalyst is to subject the gel to the action of a soluble salt of copper under conditions such that a layer of insoluble copper compound is deposited on the interior pore surface of the gel. Heretofore, attempts have been made to deposit metal compounds on silica gel but these attempts have usually not succeeded in accomplishing more than depositing the metal compound on the external surface of the silica gel grains. Because of the extremely small dimensions of the pores, which are of the order of 5 millimicrons in diameter, these are apparently plugged by precipitates and great care must be exercised to prevent the formation of a heavy precipitate. This we avoid by maintaining the gel in a slightly acid condition and the presence of basic precipitating reagents is scrupulously avoided.

Instead of preparing a silica gel, we may also employ precipitated silica which may be prepared according to the following procedure. Commercial water glass is diluted with an equal volume of distilled water and to this solution is added, with stirring, hydrochloric acid of 5 N. concentration until there is present about 20% of acid in excess of that required to neutralize the water glass. The precipitated gelatinous silica was then washed with hot distilled water until the washings tested free of chloride. About 100 grams of the moist precipitate was digested for two hours with about 3 liters of 0.1 molar copper nit 'ate solution on a steam bath. This treatment 0 uses a hydrolysis of the copper nitrate accompanied by 'a deposition of a copper compound on the surface of the silica which we bev lieve to be an adsorbed layer of active copper compound on the surface of the silica on which it is deposited.

The treated silica was washed three times by de'cantation with distilled water followed by two washings of hot water and two washings of cold 4 water on a suction funnel using about 300 m1. of water for each washing. The washed material was pelleted and finally dried at 210 to 220 F.

" in a steam heated drying oven, after which it was ready for, use as a catalyst for-promoting cracking of gas oil. It is estimated that the amount If desired, the gel may be washed only partially at first, then partly dried of copper in the dried catalyst was about 0.5 wt. per cent.

When activating the gel with copper salt, we prefer to maintain the solution slightly acid corresponding to a hydrogen ion concentration of about 2-6 pH. The hydrogen ion concentration will usually increase during the activation treatment, for example, the pH may be 4 at the start and 2.5 to 3 at the 'end of the treatment.

We prefer to employ this catalyst for the cracking of hydrocarbon oils at temperatures of about 700 to 1050 F., employing contact times of between about second to 5 minutes, preferably contact times within the range of 1 second to 1 minute. Contact time referred to is the time required for one volume of oil vapor at the condition of experiment to pass one volume of catalyst. We prefer to employ our new catalyst at relatively low pressures, for example, atmos-' pheric to 50 lbs. per square inch. gage. However,

somewhat higher pressures, e. g., 100 to 200 lbs.

per square inch may be used.

As an example of the use of the copp r-silica catalyst for the cracking of heavy petroleum oils to gasoline, several runs were made on Mid-Continent gas oil at 35.6 AP. I. gravity. The data obtained are shown in the following table:

Silica Silica 8..- .ar ar ice cop- W1 oop- Catalyst alone per and per and slightly thoroughly washed washed Cracking temperature .F. 925 925 925 Pressure Vol. of oil/vol. of catalyst/hr l. 71 1. 29 l. 3 Bbls. of oil/ton f catalyst/hr 27. 2 27. 4 30. 4 Time of contact seconds. 6.05 7. 25 7. 7 Length of run in hours 6. 03 6. 0 6. 03 Weight recovery rcent of charge" 99. 4 99. 0 90. 2 Once through yields:

Dry as weight.....percent l. 77 3.0" 2. 3 Case ine vol .do 9. 55 15.8 16. 45 Recycle stock vol .do 87.8 81. 1 R2. 4 Cubic feet of gas/gal. of gasoline" 21.2 25.0 16. 6 Specific gravity of gas 81 71 .78 Gasoline characteristics:

End point F 400 400 426 Gravity A. P. I 58.4 58.8 55.5 Knock rating 0. F. R M

(from blends) 72.6 88. 86. 3 Unsaturation percent. 81.0 75.0 .5

Atmospheric.

It will be observed from the above data that the treatment with a. copper salthas a powerful activating effect upon the silica catalyst, increasing not only the cracking rate but also the knocl:

rating of the final product. The enhanced effectiveness of the new catalyst is not easily explained. We believe, however, that when the silica gel is treated with the copper salt solution, there occurs a simultaneous adsorption and hydrolysis causing the deposition of a copper compound on the surface of the silica throughout its entire pore structure. This compound is probably an oxygen compound of copper such as copper hydroxide or more probably the copper unites to form a complex compound with. the S102 molecules and hydrated SiO-z molecules on the surface of the gel and within the pores of the grains thereof. It is believed that the molecules of SiOr at the surface present unsatisfied valences which form a chemical union with the copper and its compounds so that the gel treated with copper salt solution is substantially identical in physical structure with the untreated silica gel excepting aaoegrse than a monomolecular layer of copper compound. Furthermore, we believe that the electronic structure of the copper compound on the surface is disturbed by the unbalanced electronic structure of the S102, previously referred to as unsatisfied valence, and that in some way the peculiarly high activity of these catalysts is related to their unbalanced electronic structure, or to the molecular orientation of the copper compound.

As evidence of the hydrolysis of the copper salt on the surface of the gel, we find that the soltuion develops a definite acidity which-can only be accounted for by the following hydrolytic reaction:

We choose to call this reaction on adsorbolytic reaction, indicating that the hydrolysis or splitting of the copper salt is brought about by the adsorption phenomenon. Simultaneously, with the formation of acid in'the solution, there is deposited within the silica a measurable amount of copper compound which we have shown by analysis to vary between about 0.1 to 2% 0i cop per, depending partly on the concentration of copper salt solution employed, the hydrogen ion concentration in the solution, and the method of treatment.

Although we prefer to use a copper salt solution of about 0.1 molar concentration, this may be varied over a considerable range without greatly affecting the amount of copper deposited within the gel. Thus, we may use concentrations from about 0.02M. to 1.5 M., if desired. We may increase the amount of copper hydrolyzed by various methods. For example. we may add a buffer salt to the solution, such as copper acetate for the purpose of regulating the pH value of the solution, care being taken to avoid pH values which might result in the precipitation of insoluble copper compounds bydouble decomposition. We may also repeat the treatment of the gel with copper solution of the same or different concentrations, or we mayperform the treatment in a flowing stream. The copper salt solution may be made to flow through a series of beds of the gel in rotation so that the most nearly spent solution serves to contact the fresh gel, thus adsorbing the greater amount of the copper from the solution In the previous description, the freshly prepared silica was dried after washing and before treating with the copper solution. However, it is sometimes desirable to omit this drying step. The freshly made silica which has been thoroughly'washed may be immediately treated with the copper solution and then, dried. In this case, howevena longer time is required for diffusion of the solution into the larger pieces of the silica.

As indicated above, the catalyst may be regenerated after it has become fouled with carbonaceous deposits in *the cracking operation. Regeneration is most conveniently accomplished by passing a stream of air and inert gas, for example, steam, through the catalyst bed, care being taken to control the oxygen concentration of the regenerating gas so that the combustion temperature is kept below about 1200 F. and preferably below about 1100" F. Excessive heating above these temperatures causes catalyst deterioration. The regenerated catalyst has a bluish color, evidence that the copper is present in the form of some peculiar; adsorption compound and not as copper oxide which is black.

After regeneration, the cracking may be cont nned. The duration of cracking between regeneration periods may be about hours but this depends largely on the nature of the stock being cracked. Ifthe stock cracked is a residual oil containing asphaltic matter, the duration of cracking is considerably less before catalyst activity is seriously reduced. Thus, with a typical Mid-Continent residual oil of about 22 A. P. I.

gravity, the catalyst may be used for a period of about 30 minutes to 2 hours between regeneraations. When using gas oil, we have found that in a typical operation the catalyst activity has decreased about 25% to 50% in a period of 6 hours. In the case of residual oils or Very heavy distillate charging stocks, we may initially crack the oilin one catalyst bed and produce intermediate boiling hydrocarbons with very little gasoline. Then we may pass the vapors directly into a second catalyst bed with-or without heating to a higher temperature to complete the cracking. The extent or depth of cracking per pass depends partly on the freshness of the catalyst and on the temperature. If desired, the process may be conducted to produce from gas oil about 45% to 55% of gasoline in a single pass and the uncracked products heavier than gasoline may be either recycled in the operation or cracked in a secondary cracking operation. Alternatively, the extent of cracking may be maintained about to 30% and the uncracked heavy products may be recycled until completely cracked, the only products being gasoline and gas. Carbonaceous matter produced in the operation, is deposited on the catalyst and removed in regeneration.

If desired, we may employ the catalyst in moving bed apparatus in whichla portion of the spent catalyst is continuously withdrawn and regenerated externally, fresh and/Or regenerated catalyst being supplied continuously to the apparatus. We may also employ the catalyst in finely divided form. For example, the catalyst may be finely divided by grinding and supplied as a slurry in oil to the cracking chamber or coil or introduced as a powder into the vapor stream. In this type of operation, the spent catalyst is settled or filteredfrom the products and separately regenerated.

Although we have given specific examples of methods of preparing the catalyst and have described its use in certain cracking operations, We intend that our invention be limited only by the following claims.

We claim:

1. The process of converting heavy hydrocar- "bon oils into gasoline, comprising vaporizing said oils and subjecting the vapors at a temperature between about 700 and 1050 F. to the action-of a catalyst consisting essentially of silica gel promoted with copper produced by treating said gel with a copper compound in an acid solution and thereafter washing and drying.

2. The process of converting heavy hydrocarbon oils into gasoline which comprises vaporizing said oils and subjecting the vapors at a temperature between about 700 and 1050 F. to the action of a catalyst comprising freshly precipitated silica activated by a uniformly adsorbed film of a copper compound, said catalyst containing about 0.1 to 2% of copper, adsorbed from an acid solution of a copper salt.

3. The process of converting hydrocarbon oils into gasoline which comprises vaporizing said oils and subjecting the vapors thereof at a conversion temperature to the action of a catalyst prepared by precipitating active silica by the action of a substantial excess of inorganic acid on a ilicate, treating said active silica with an acid solution of a copper salt whereby a copper compound is adsorbed thereon and thereafter drying the treated silica catalyst.

4. The process of claim 1 wherein said acid solution has a hydrogen ion concentration within 

